CN113732422B - Brazing flux-free brazing method and brazing filler metal paste for aluminum alloy - Google Patents
Brazing flux-free brazing method and brazing filler metal paste for aluminum alloy Download PDFInfo
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- CN113732422B CN113732422B CN202111114679.3A CN202111114679A CN113732422B CN 113732422 B CN113732422 B CN 113732422B CN 202111114679 A CN202111114679 A CN 202111114679A CN 113732422 B CN113732422 B CN 113732422B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K1/00—Soldering, e.g. brazing, or unsoldering
- B23K1/002—Soldering by means of induction heating
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K3/00—Tools, devices, or special appurtenances for soldering, e.g. brazing, or unsoldering, not specially adapted for particular methods
- B23K3/04—Heating appliances
- B23K3/047—Heating appliances electric
- B23K3/0475—Heating appliances electric using induction effects, e.g. Kelvin or skin effects
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K3/00—Tools, devices, or special appurtenances for soldering, e.g. brazing, or unsoldering, not specially adapted for particular methods
- B23K3/06—Solder feeding devices; Solder melting pans
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
- B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
- B23K35/24—Selection of soldering or welding materials proper
- B23K35/28—Selection of soldering or welding materials proper with the principal constituent melting at less than 950 degrees C
- B23K35/282—Zn as the principal constituent
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Abstract
The invention belongs to the field of brazing materials, and particularly relates to a brazing flux-free brazing method and brazing paste for aluminum alloy. The brazing method of the aluminum alloy without the brazing flux comprises the following steps: (1) Galvanizing the surface to be galvanized of the aluminum alloy to form a galvanized layer; (2) Coating brazing filler metal paste without brazing flux on a zinc coating, wherein the brazing filler metal paste without brazing flux consists of a binder and the following components in parts by weight: 70-80 parts of zinc-aluminum brazing filler metal and 6.0-8.0 parts of rubidium-iron-boron magnetic particles; (3) Heating the part to be soldered to form eutectic or near-eutectic solder liquid between the zinc coating and the zinc-aluminum solder, applying a rotating magnetic field, and enabling the rubidium-iron-boron magnetic particles to perform self-spinning motion under the action of the rotating magnetic field to solder and connect the aluminum alloy without soldering flux. In the invention, the plating layer and the brazing filler metal layer are diffused under the action of concentration gradient, and the aluminum alloy brazing filler metal-free brazing is realized under the conditions of spin film breaking and flow promotion of strong magnetic particles; the obtained soldered joint has less inclusions and air hole defects, compact soldering seam and high joint strength.
Description
Technical Field
The invention belongs to the field of brazing materials, and particularly relates to a brazing flux-free brazing method and brazing paste for aluminum alloy.
Background
The cast aluminum alloy has low manufacturing cost, light weight, high strength and good low-temperature performance, and is widely applied to aerospace, ships, automobiles, motorcycles and large-scale equipment. The cast aluminum alloy is easy to generate defects such as oxide inclusion, air holes, shrinkage porosity, cracks and the like in the casting process. Because of the defects of the cast aluminum alloy casting, the welding defects such as inclusion, air holes, cracks and the like are easy to generate in the brazing process.
At present, the commonly used brazing method for casting aluminum alloy is that Zn95Al brazing filler metal is matched with cesium fluoroaluminate brazing flux to carry out induction or flame brazing in the atmosphere. Zn95Al is eutectic solder (the solder with the Zn content of 95 percent is the eutectic solder, and the solder with the Zn content of less than 95 percent is hypoeutectic solder), has good flowing property and low soldering temperature, and is widely used for soldering and casting aluminum alloy. However, the main components of the cesium fluoroaluminate brazing flux matched with the Zn95Al eutectic brazing filler metal are CsF and Al 3 F, the viscosity is high, the brazing residues are difficult to remove, and defects such as excessive slag inclusion, air holes and the like are further formed in brazing seams, so that the joint strength is low, and the service life of a casting is influenced.
Disclosure of Invention
The invention aims to provide a brazing flux-free brazing method for aluminum alloy, which reduces inclusions and air holes and improves joint strength.
A second object of the present invention is to provide a solder paste that matches the use of the above method.
In order to achieve the purpose, the technical scheme of the brazing method without the brazing flux for the aluminum alloy is as follows:
a fluxless brazing method for aluminum alloys, comprising the steps of:
(1) Galvanizing the surface to be galvanized of the aluminum alloy to form a galvanizing coat;
(2) Coating brazing filler metal paste without brazing flux on a zinc coating, wherein the brazing filler metal paste without brazing flux consists of a binder and the following components in parts by weight: 70-80 parts of zinc-aluminum brazing filler metal and 6.0-8.0 parts of neodymium iron boron magnetic particles; the zinc-aluminum brazing filler metal consists of the following components in parts by weight: 80.0 to 90.0 portions of Zn and 5.0 to 15.0 portions of Al;
(3) Heating the part to be welded to enable the zinc coating and the zinc-aluminum brazing filler metal to form eutectic or near-eutectic brazing filler metal liquid, applying a rotating magnetic field, enabling the neodymium iron boron magnetic particles to perform spinning motion under the action of the rotating magnetic field, and brazing and connecting the aluminum alloy without brazing flux.
The invention relates to a soldering flux-free brazing method for casting aluminum alloy, which is characterized in that a coating and a brazing filler metal layer are diffused under the action of concentration gradient, and the soldering flux-free brazing of the aluminum alloy is realized under the conditions that strong magnetic particles are rotated to break membranes and flow is promoted; the obtained soldered joint has less inclusions and air hole defects, compact soldering seam and high joint strength.
Preferably, in the step (1), the thickness of the zinc plating layer is 15 to 30 μm.
Preferably, the particle size of the neodymium iron boron magnetic particles is 30-50 nm. Neodymium-iron-boron magnetic particles, namely neodymium-iron-boron magnets (Nd 2Fe 14B), are tetragonal crystals formed by neodymium, iron and boron, and belong to strong magnetic materials; another reason for selecting the ndfeb magnetic particles is that they have good wettability to the solder and do not affect the interfacial bonding with the solder.
Preferably, the weight ratio of the zinc-aluminum solder to the binder is (70.0-80.0) to (3.0-6.0); the binder is one or the combination of more than two of polyethylene glycol 200, terpineol and isopropanol. More preferably, the coating thickness of the solder paste is 3 to 8 μm.
Preferably, in step (3), the rotating magnetic field is generated by alternating current, the current intensity is 0.1-20A, and the current frequency is 10 2 -10 5 Hz。
Preferably, in the step (3), the time for applying the rotating magnetic field is 8 to 15S.
Preferably, in the step (3), the brazing temperature is 380-420 ℃.
More preferably, the aluminum alloy is a cast aluminum alloy. The cast aluminum alloy has wide application, a plurality of defects are accompanied in the casting process, the conventional brazing connection effect is poor, and the method can well solve the brazing connection problem of the cast aluminum alloy.
The technical scheme of the solder paste is as follows:
the brazing filler metal paste for aluminum alloy brazing without the brazing flux consists of a binder and the following components in parts by weight: 70-80 parts of zinc-aluminum brazing filler metal and 6.0-8.0 parts of neodymium iron boron magnetic particles; the zinc-aluminum brazing filler metal consists of the following components in parts by weight: 80.0 to 90 portions of Zn and 5.0 to 15.0 portions of Al.
The brazing filler metal paste for brazing the aluminum alloy without the brazing flux is used in cooperation with the brazing method, can realize rapid induction brazing of cast aluminum alloy in an atmospheric environment, does not pollute the environment, and is green and environment-friendly.
Drawings
FIG. 1 is a schematic view of the assembly of a brazing structure of the fluxless brazing method for aluminum alloys according to the present invention;
FIG. 2 is a left side view of FIG. 1;
FIG. 3 is a prior art braze joint topography with a flux braze;
FIG. 4 is a view showing the appearance of a brazing seam in brazing-free brazing in example 5 of the present invention;
FIG. 5 is a part of a shear strength test piece of example 5 of the present invention;
FIG. 6 is the spectrum analysis result of the A point inclusion in the brazing seam of the brazed joint with flux in the prior art;
wherein, 1-casting aluminum alloy, 2-zinc layer, 3-solder paste and 4-magnetic pole.
Detailed Description
The brazing method of the aluminum alloy without the brazing flux is mainly characterized in that the high-reliability and high-density brazing flux of the aluminum alloy is realized by means of a concentration gradient diffusion principle and a self-rotating film breaking mechanism of neodymium iron boron strong magnetic particles under the action of a rotating magnetic field.
The following brazing method is mainly implemented according to the following steps:
step one, coating a pure zinc layer on the surfaces of two to-be-welded cast aluminum alloys to obtain a galvanized cast aluminum alloy;
step two, uniformly coating a layer of brazing filler metal paste on the coating of one of the galvanized cast aluminum alloys, compounding the brazing filler metal paste with the coating surface of the other cast aluminum alloy, assembling and fixing the brazing filler metal paste, placing the assembly and the fixation in a rotating magnetic field, and placing the part to be welded in an inductor;
turning on a power supply, starting heating to 380-420 ℃, enabling the brazing filler metal layer to be in a liquid state, and carrying out diffusion dissolution with the plating layers on the two sides under the action of concentration gradient to form eutectic or near-eutectic brazing filler metal liquid;
and step four, keeping the brazing filler metal in a liquid state, starting a spinning magnetic field to enable neodymium iron boron strong magnetic particles in the brazing filler metal layer to spin and move, colliding and rubbing, enabling the brazing filler metal to flow for filling, forming metallurgical bonding, turning off a magnetic field power supply, stopping a heating power supply, and finishing brazing.
As shown in FIG. 1, in the above method, a pure zinc layer 2 is coated on the surface of each of two aluminum alloys 1 to be cast, a hypoeutectic Zn-Al braze paste 3 containing neodymium, iron and boron and strong magnetic particles is coated on one of the aluminum alloy coatings, and the aluminum alloy coatings are oppositely assembled with the other aluminum alloy coating surface. During brazing, a workpiece is placed in a spinning magnetic field, and a part to be welded is placed in the inductor. When the temperature is heated to 382-420 ℃, the brazing filler metal layer is melted into brazing filler metal liquid, and under the action of concentration gradient, the brazing filler metal liquid and the coating are diffused to generate eutectic reaction to form eutectic Zn95Al brazing filler metal liquid. And starting a spinning magnetic field, enabling the strong magnetic particles to spin and rub and impact the surface of the coating, breaking a film and assisting flow, promoting the flowing joint filling of the brazing filler metal liquid, and realizing the brazing without the brazing flux of the cast aluminum alloy.
Near eutectic solders refer to solders that are near eutectic compositions. The zinc-aluminum solder components (Zn 80.0-90.0 parts and Al5.0-15.0) in the solder paste are hypoeutectic solder, when the solder paste is heated to the temperature of 380-420 ℃, zn in a coating continuously diffuses into a solder layer, so that the content of Zn in the solder is increased, the solder components are closer to eutectic components (95 Zn5 Al), and near-eutectic solder liquid can be formed.
The rotating magnetic field is produced by a transverse magnetic field generator, is designed according to the principle that a rotating magnetic field is produced by symmetrical three-phase alternating current in symmetrical three-phase windings, mainly comprises an iron core and windings, and is mainly characterized in that the intensity of the magnetic field is unchanged, and the direction of the magnetic field continuously rotates.
Specifically, as shown in fig. 1 and 2, three pairs of magnetic poles 4 are uniformly distributed on the same circumference (a brazing workpiece is placed inside a magnetic field formed by the three pairs of magnetic poles), the central axes of the three pairs of magnetic poles 4 uniformly distributed pass through the center of a weld joint, and excitation coils on the magnetic poles are sequentially supplied with power by three-phase single-six-beat excitation, so that a rotating magnetic field is generated. The current intensity is 0.1-20A, and the current frequency is 10 2 -10 5 Hz, and the time is 8-15S.
The rotating magnetic field rotates clockwise or counterclockwise in a plane perpendicular to the surface to be welded. In the left view of fig. 2, the magnetic field rotation direction may be clockwise or counterclockwise.
The invention does not need soldering flux, and no soldering flux remains in the soldering seam; in addition, the self-rotating impact (reciprocating motion) of the neodymium iron boron strong magnetic particles can further play a role in deslagging and degassing, and the obtained joint is compact and high in strength.
The following examples are provided to further illustrate the practice of the invention. The following examples are merely illustrative of the present invention and should not be construed as limiting the scope of the invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are conventional products which are commercially available, and are not indicated by manufacturers.
1. Specific examples of fluxless brazing method for casting aluminum alloy
Example 1
The brazing method of the aluminum alloy of the embodiment comprises the following steps:
(1) Plating a pure zinc layer with the thickness of 15-30 mu m on the surfaces to be welded of the two cast aluminum alloys to obtain galvanized cast aluminum alloys;
(2) Uniformly coating a layer of brazing filler metal paste with the thickness of 3-8 mu m on the coating of one of the cast aluminum alloys, oppositely matching the coating surface of the other cast aluminum alloy, fixing the brazing filler metal paste, placing the brazing filler metal paste in a rotating magnetic field, and placing the part to be welded in an inductor;
the solder paste comprises the following components in parts by weight: 75.0 parts of solder powder, 6.0 parts of neodymium iron boron strong magnetic particles and 3.0 parts of binder. The solder powder comprises the following components in parts by weight: 80.0 parts of Zn and 5.0 parts of Al. The particle size of the neodymium iron boron strong magnetic particles is 30nm. The binder is polyethylene glycol 200.
(3) Turning on a power supply, starting heating to 400 ℃, and carrying out diffusion dissolution on the brazing filler metal layer and the plating layers on the two sides under the action of concentration gradient to form eutectic brazing filler metal liquid;
(4) Keeping the brazing filler metal in a liquid state, starting a rotating magnetic field to enable the neodymium iron boron strong magnetic particles in the brazing filler metal layer to perform spinning movement, and stopping a Guan Cichang power supply to heat the power supply when the brazing filler metal flows for joint filling and metallurgical bonding is formed, so that the brazing is completed.
In this embodiment, three pairs of magnetic poles are uniformly distributed on the same circumference and all three pairs of magnetic poles are uniformly distributedThe central axis of the cloth passes through the center of the welding seam, and the excitation coils on the magnetic poles are supplied with power by adopting a three-phase single six-beat excitation sequence, so that a rotating magnetic field is generated. The current intensity is 10A, and the current frequency is 10 4 Hz, time 10S.
In other embodiments, the current intensity may be varied from 0.1, 0.5, 1, 3, 5, 8, 15, 20A and the current frequency may be 10A depending on the brazing conditions 2 、10 3 、10 5 Hz is different, the time can be different from 8 s, 12 s and 15s, so that the magnetic particles can reciprocate and the film breaking and flow aiding are favorable.
Example 2
The aluminum alloy of this example was brazed without flux substantially as in example 1, except that: the solder paste comprises the following components in parts by weight: 76.0 parts of solder powder, 7.0 parts of neodymium iron boron strong magnetic particles and 5.0 parts of binder. The material powder comprises the following components in parts by weight: 82.0 parts of Zn and 8.0 parts of Al. The particle size of the neodymium iron boron strong magnetic particles is 40nm. The binder is terpineol.
Example 3
The aluminum alloy of this example was brazed without flux substantially as in example 1, except that: the solder paste comprises the following components in parts by weight: 77.0 parts of brazing filler metal powder, 8.0 parts of neodymium iron boron strong magnetic particles and 6.0 parts of binder. The solder powder comprises the following components in parts by weight: 85.0 parts of Zn and 10.0 parts of Al. The particle size of the neodymium iron boron strong magnetic particles is 50nm. The binder is isopropanol.
Example 4
The aluminum alloy of this example was brazed without flux substantially as in example 1, except that: the solder paste comprises the following components in parts by weight: 78.0 parts of solder powder, 6.0 parts of neodymium iron boron strong magnetic particles and 3.0 parts of binder. The solder powder comprises the following components in parts by weight: 87.0 parts of Zn and 12.0 parts of Al. The particle size of the neodymium iron boron strong magnetic particles is 30nm. The adhesive consists of terpineol and isopropanol, and the volume ratio of the terpineol to the isopropanol is 1:1.
Example 5
The aluminum alloy of this example was brazed without flux substantially as in example 1, except that: the solder paste comprises the following components in parts by weight: 79.0 parts of brazing filler metal powder, 7.0 parts of neodymium iron boron strong magnetic particles and 5.0 parts of binder. The solder powder comprises the following components in parts by weight: 88.0 parts of Zn and 14.0 parts of Al. The particle size of the neodymium iron boron strong magnetic particles is 50nm. The binder consists of polyethylene glycol 200 and terpineol according to the volume ratio of 1:1.
Example 6
The aluminum alloy of this example was brazed without flux substantially as in example 1, except that: the solder paste comprises the following components in parts by weight: 70.0 parts of brazing filler metal powder, 8.0 parts of neodymium iron boron strong magnetic particles and 6.0 parts of binder. The solder powder comprises the following components in parts by weight: 90.0 parts of Zn and 15.0 parts of Al. The particle size of the neodymium iron boron strong magnetic particles is 40nm. The binder consists of polyethylene glycol 200, terpineol and isopropanol in a volume ratio of 1.
In other embodiments of the fluxless brazing method of the present invention, the brazing temperature can be controlled to 385 deg.C, 395 deg.C, 405 deg.C, 415 deg.C, 420 deg.C, etc., all of which can achieve substantially equivalent experimental results.
2. Specific examples of solder pastes
Example 7
The brazing filler metal paste for aluminum alloy fluxless brazing of the present example corresponds to the brazing filler metal paste in the brazing method of example 1.
Other examples of the solder paste correspond to the solder pastes in the soldering methods of examples 2 to 6, respectively.
3. Examples of the experiments
Experimental example 1
Under the same other conditions, the Zn95Al eutectic brazing filler metal is matched with cesium fluoroaluminate brazing flux to carry out flux-containing induction brazing on cast aluminum alloy, and the brazing method of the embodiment 5 is additionally adopted to carry out fluxless induction brazing on cast aluminum alloy, so that the brazing seam appearance and the joint strength of two joints are compared.
The appearance of the brazing seam with the brazing flux is shown in FIG. 3, and the appearance of the brazing seam without the brazing flux is shown in FIG. 4.
As can be seen from the comparison of the appearance of the brazing seams, compared with the brazing seams without the brazing flux, the brazing seams obtained by brazing with the brazing flux have more inclusions and air holes.
The cast aluminum alloy welding test base material was a plate having a thickness of 2mm, a width of 15mm and a length of 50mm, processed into a standard shear specimen according to the specification of GB/T11364-2008 after brazing, and the shear strength of the comparative joint was measured, and the results are shown in Table 1.
The shear strength pair ratios for the two joints are shown in table 1. The partial shear strength test piece conditions are shown in fig. 5.
TABLE 1 shear Strength of two joints
It can be seen that the mean shear strength of the flux-free braze seams, i.e. those of example 1, is 44.7MPa, whereas the mean shear strength of the seams obtained with flux brazing is only 21.8MPa, the former being much higher than the latter.
The shear strength of the joints of examples 1 to 6 is shown in table 2.
TABLE 2 shear Strength of joints of examples 1 to 6
| Average joint strength/MPa | |
| Example 1 | 30 |
| Example 2 | 32 |
| Example 3 | 35.6 |
| Example 4 | 38.5 |
| Example 5 | 44.7 |
| Example 6 | 52 |
| Zn95Al solder with flux seam | 21.8 |
As can be seen from table 2, the shear strength of the joints obtained by the methods of the examples was significantly improved compared to the Zn95Al brazing filler metal with flux brazing.
Experimental example 2
The energy spectrum analysis of inclusions in the flux seams is shown in FIG. 6.
As can be seen from FIG. 6, the spectrum analysis result of the point A in the flux brazing seam contains Cs and F components, which proves that the flux brazing seam has more flux residues and is difficult to remove completely, and the brazing strength of the flux brazing seam is difficult to effectively improve.
Claims (9)
1. A fluxless brazing method for aluminum alloys, comprising the steps of:
(1) Galvanizing the surface to be galvanized of the aluminum alloy to form a galvanized layer;
(2) Coating brazing filler metal paste without brazing flux on a zinc coating, wherein the brazing filler metal paste without brazing flux consists of a binder and the following components in parts by weight: 70-80 parts of zinc-aluminum solder and 6.0-8.0 parts of neodymium iron boron magnetic particles; the zinc-aluminum brazing filler metal consists of the following components in parts by weight: 80.0 to 90.0 parts of Zn and 5.0 to 15.0 parts of Al;
(3) Heating the part to be welded to enable the zinc coating and the zinc-aluminum brazing filler metal to form eutectic or near-eutectic brazing filler metal liquid, applying a rotating magnetic field, enabling the neodymium iron boron magnetic particles to perform spinning motion under the action of the rotating magnetic field, and brazing and connecting the aluminum alloy without brazing flux.
2. The brazing method of an aluminum alloy according to claim 1, wherein in the step (1), the thickness of the zinc plating layer is 15 to 30 μm.
3. The fluxless brazing method for aluminum alloy according to claim 1, wherein the diameter of the neodymium iron boron magnetic particles is 30 to 50nm.
4. The method of brazing without flux of an aluminum alloy as in any one of claims 1~3 wherein the weight ratio of the zinc-aluminum solder to the binder is (70.0 to 80.0): (3.0 to 6.0); the binder is one or more than two of polyethylene glycol 200, terpineol and isopropanol.
5. A method of fluxless brazing of aluminum alloy according to claim 4, wherein the paste is applied to a thickness of 3~8 μm.
6. The method for fluxless brazing of aluminum alloy according to claim 1, wherein in the step (3), the rotating magnetic field is generated by an alternating current having a current intensity of 0.1 to 20A and a current frequency of 10 2 -10 5 Hz。
7. The method for fluxless brazing of aluminum alloy according to claim 6, wherein in the step (3), the rotating magnetic field is applied for a time of 8 to 15S.
8. A method for fluxless brazing of aluminum alloy according to claim 1, wherein the heating temperature in the step (3) is 380 to 420 ℃.
9. A method of fluxless brazing of aluminum alloy according to claim 1 or 6 or 7 or 8, wherein the aluminum alloy is a cast aluminum alloy.
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| CN202111114679.3A CN113732422B (en) | 2021-09-23 | 2021-09-23 | Brazing flux-free brazing method and brazing filler metal paste for aluminum alloy |
| PCT/CN2021/135210 WO2023045083A1 (en) | 2021-09-23 | 2021-12-03 | Method for flux-free soldering of aluminum alloy, and solder paste |
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| CN202111114679.3A CN113732422B (en) | 2021-09-23 | 2021-09-23 | Brazing flux-free brazing method and brazing filler metal paste for aluminum alloy |
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| CN115255714B (en) * | 2022-08-22 | 2023-04-28 | 河南科技大学 | Strong magnetic particle reinforced flux-cored solder and preparation method thereof |
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| CN102350623A (en) * | 2011-08-31 | 2012-02-15 | 金龙精密铜管集团股份有限公司 | Manufacturing method for aluminum alloy heat exchanger |
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| CN102350623A (en) * | 2011-08-31 | 2012-02-15 | 金龙精密铜管集团股份有限公司 | Manufacturing method for aluminum alloy heat exchanger |
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